US4499223A - Hydrolyzable polyester resins and coating compositions containing the same - Google Patents
Hydrolyzable polyester resins and coating compositions containing the same Download PDFInfo
- Publication number
- US4499223A US4499223A US06/602,722 US60272284A US4499223A US 4499223 A US4499223 A US 4499223A US 60272284 A US60272284 A US 60272284A US 4499223 A US4499223 A US 4499223A
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- metal
- acid
- resin
- varnish
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
- C09D5/165—Macromolecular compounds containing hydrolysable groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/681—Polyesters containing atoms other than carbon, hydrogen and oxygen containing elements not provided for by groups C08G63/682 - C08G63/698
Definitions
- Polyester resins derived from polycarboxylic acids and polyhydric alcohols have been widely used as resinous vehicle in coatings, because an excellent film with toughness and other desirable properties can be obtained therefrom. Irrespective of the polymerization degree, the ester bondings contained are resistive against hydrolysis, which in turn, is believed to be one of the reasons and advantages of using this polymer as resinous component.
- polyester resin may be advantageously prepared by the reaction of polycarboxylic acid and polyhydric alcohol, a part of which is a metallic salt of hydroxy carboxylic acid of the formula (I):
- acids are straight chain dicarboxylic acids as oxalic acid, succinic acid, succinic anhydride, adipic acid, azelaic acid and sebasic acid; aromatic acids as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, terephthalic anhydride, hexahydro phthalic acid, hexahydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic acid, trimellitic anhydride, pyromellitic acid and pyromellitic anhydride; and unsaturated dicarboxylic acids as maleic acid, maleic anhydride, fumaric acid and itaconic acid.
- monocarboxylic acid as benzoic acid, p-t-butyl benzoic acid, and various fatty acids of animal and vegetable fats and oils may be added as molecular regulator.
- the metal salts of hydroxy acids to be reacted, as at least part of polyhydric alcohol component, with the abovesaid acid component may be represented by the formula (I)
- R, l and M are as defined above.
- the hydrocarbon aresidue R may be of saturated or unsaturated, straight or branched, aliphatic or aromatic type.
- a is an integer from 1 to 38.
- R 1 and R 2 each represents a member selected from hydrogen atom, alkyl having 1 to 10 carbon atoms and alkene having 2 to 10 carbon atoms, and m and n each is 0 or an integer from 1 to 16.
- said R 1 and R 2 each stands for hydrogen atom or alkyl having 1 to 8 carbon atoms, and m and n each is 0 or an integer from 1 to 10.
- hydroxy carboxylic acid of this type are lactic acid, hydacrylic acid, 12-hydroxy stearic acid and glycolic acid.
- b is an integer from 2 to 38.
- R 3 and R 4 each represents a member selected from hydrogen atom, alkyl having 1 to 10 carbon atoms and alkene having 2 to 10 carbon atoms, and x, y and z each is 0 or an integer from 1 to 10.
- said R 3 and R 4 each represents a member selected from hydrogen atom and alkyl having 1 to 8 carbon atoms, x is 0 or an integer from 1 to 4, y is 0 or an integer from 1 to 6 and z is 0 or an integer from 1 to 10.
- Examples of hydroxy carboxylic acids of this type are ricinoleic acid and ricinoelaidic acid.
- R 7 is a member selected from alkylene having 2 to 8 carbon atoms and ether bonding bearing alkylene having 4 to 8 carbon atoms
- R 8 is a member selected from saturated and unsaturated cyclic hydrocarbons having 6 to 7 carbon atoms.
- particularly preferred members are lactic acid, glycolic acid, hydracylic acid and 12-hydroxy stearic acid.
- the progress of polycondensation may be traced by checking the amount of water generated and the acid value of the product obtained.
- polymerization should preferably be stopped at a relatively earlier stage, thereby producing a lower molecular weight, solvent soluble type product.
- the degree of polycondensation, optimum molecular weight of the polymer, and control of said reaction are, however, patent to those skilled in the art and hence, no additional explanation would be required.
- the end point of the reaction is customarily determined by checking the amount of water generated, acid value of the product or the like, and after completion of the reaction, the mixture is diluted with an organic solvent as aromatic hydrocarbons (e.g. toluene, xylene), ketones (e.g.
- esters e.g. ethyleneglycol monoethyl ether acetate, butyl acetate, ethyl acetate
- alcohols e.g. n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol
- ethers e.g. 1,4-dioxane, tetrahydrofuran
- mixtures thereof to the desired solid content and used as resinous vehicle or varnish as it is.
- the coating should preferably be hydrolyzed or dissolved out at a rate of 10 ⁇ 350 ⁇ /year and more preferably 20 ⁇ 250 ⁇ /year.
- the hydrolysis rate is the most important factor and the term "hydrolysis rate" as used herein denotes the speed whereby the coating is hydrolyzed and dissolved out in sea water.
- the present hydrolyzable polyester resins are ideal and that the metal content should be in the order of 0.3 ⁇ 10 wt%, preferably 0.6 ⁇ 8 wt% and most preferably 0.6 ⁇ 5 wt%, of the total polymer weight. If the metal content is less than the lower limit of 0.3%, the hydrolysis rate is too slow to attain the object of this invention. Whereas, if it is more than the upper limit of 10 wt%, hydrolysis rate is too fast, and it is unable to obtain a durable coating for a longer period of time.
- the polyester resin should preferably have an acid value of 2 to 80, more preferably 5 to 75, and Tg of -10° ⁇ 60° C., more preferably -5° ⁇ 40° C. and most preferably -5° ⁇ 25° C.
- the present novel polyester resin thus can afford an ideal marin paint composition, whose coating is gradually hydrolyzed and dissolved out in sea water in optimum rate, while maintaining the characteristics film performance in practical use. Moreover, the metal liberated per se is useful as toxicant for marine livings.
- any of the conventional techniques may be satisfactorily used as they are.
- any of the common organic solvent may be used, including aromatic hydrocarbons (e.g. toluene, xylene), ketones (e.g. methylethyl ketone, methyl isobutyl ketone), esters (e.g. ethyleneglycol monoethyl ether acetate, butyl acetate), alcohols (e.g. butyl alcohol), ethers (e.g. 1,4-dioxane, tetrahydrofuran) and the like.
- aromatic hydrocarbons e.g. toluene, xylene
- ketones e.g. methylethyl ketone, methyl isobutyl ketone
- esters e.g. ethyleneglycol monoethyl ether acetate, butyl acetate
- alcohols e.g. butyl alcohol
- ethers e.g. 1,
- the solvent needs not completely dissolve the resinous material, various other solvents employed in the coating area may be satisfactorily used.
- the solvent can be monomer or other resinous varnish.
- conventional coloring matter, coating additives or the like with the composition of this invention.
- the paint can be formulated with the present resinous varnish only.
- the antifouling purpose it is often desired or preferred to formulate the composition with the present varnish and other antifouling agent.
- the amounts of these materials may be selected in any desired levels, providiang giving no adverse effect on the film-forming of the resinous vehicle of the present invention.
- the present coating composition has the characteristics such that after coating, gradual hydrolysis and decomposition of the coating is occured and hence the antifouling agent conatained in the film can be effectively utilized to the last.
- the conventional type of composition only the toxicant contained in the vicinity of film surface is utilized for the intended object through diffusion and dissolution thereof.
- the coating turns to skelton structure with the dissolution of antifouling agent, whereas in the present coating, in the present coating, the coating is getting smoother and flatter with sailing, and the antifouling effect continues to last for a longer period of time as compared with those of the conventional one.
- the antifouling paint of the present invention is quite unique and will change the established antifouling concept in near future.
- Example 1 The same procedures as stated in Example 1 or 2 were repeated excepting using the materials shown in Table 1 to obtain hydrolyzable polyester resins and resinous varnishes V-3 to V-7.
- Example 2 The same procedures as stated in Example 1 were repeated excepting using 104 parts of Cu 12-HO stearate, 233.5 parts of phthalic anhydride, 111.5 parts of neopentylglycol and 51 parts of trimethylol ethane, to obtain a dark green resin having MW 1600, Tg 0° C., acid value 21 and Cu content 1.7 wt %. 60 Parts of thus obtained aresin were dissolved in 40 parts of xylene to obtain a resinous varnish V-8.
- Example 2 The same procedures as stated in Example 1 were repeated excepting using 21 parts of nickel lactate (in place of Cu 12-OH stearate), 264 parts of phthalic anhydride, 67 parts of neopentylglycol and 29.6 parts of trimethylol ethane.
- Example 2 Into the similar reaction vessel as used in Example 1, were placed 14.4 parts of neopentyl glycol and 46.8 parts of phthalic anhydride and the mixture was heated to 110° C. Next, 19.2 parts of trimethylol ethane and 15.1 parts of 12-hydroxy stearate were added and the mixture was heated to 140° C. and maintained at the same temperature for 30 minutes. At this stage, the resinous material showed an acid value of 208. To this, were added 4.9 parts of copper hydroxide and the mixture was heated at 140° C. while removing the formed water therefrom, for 2 hours.
- Example 1 Into the similar reaction vessel as used in Example 1, were placed 39.4 parts of phthalic anhydride, 13.3 parts of succinic anhydride, 7.1 parts of diethylene glycol, 16.6 parts of neopentyl glycol and 16.3 parts of trimethylol methane and the mixture was heated to 130° C. and maintained at the same temperature for 30 minutes. At this stage, the resinous material showed an acid value of 200. To this, were added 7.4 parts of copper hydroxide and after maintaining the temperature at 130° C. for 2 hours, the mixture was added with 4 parts of dibutyl tin oxide and 5 parts of toluene and reacted as in Example 1.
- varnish V-12 showed viscosity R and solid content 6.3%. It was found that the polyester resin contained had the characteristics of number-average molecular weight 1600, Tg 3° C., Cu 4.4 wt% and Sn 2.7 wt%.
- Example 2 Into the similar reaction vessel as used in Example 1, were placed 54 parts of phthalic anhydride, 31.4 parts of neopentyl glycol and 6 parts of trimethylol ethane and the mixture was heated to 140° C. and maintained at the same temperature for 30 minutes. At this stage, the resinous material showed an acid value of 218. To this, were added 8.6 parts of dibutyl tin oxide and 5 parts of toluene and the mixture was reacted as in Example 12, while removing the formed water under refluxing. Thus obtained resin showed an acid value of 15, Tg of 21° C. and number-average molecular weight of 1200 and had a pale yellow color. Sn content of the resin was 3.8 wt%. 60 Parts of the resin were added with 30 parts of xylene and 10 parts of butyl acetate to obtain a resinous varnish V-13.
- a resinous varnish V-14 was prepared by adding 30 parts of xylene and 10 parts of methyl isobutyl ketone to 60 parts of said resin.
- a comparative varnish 1 was prepared by using 58.1 parts of phthalic anhydride, 12.1 parts of neopentyl glycol, 9.6 parts of 1,6-hexanediol and 20.5 parts of tri-methylol ethane. This varnish had a solid content of 50.4%, Gardner viscosity of P and acid value of solid of 9.7.
- Example 2 Into the similar reaction vessel as used in Example 1, were placed 47.5 parts of phthalic anhydride, 10.1 parts of neopentyl glycol and 12.1 parts of trimethylol ethane and the mixture was heated to 140° C. and maintained at the same temperature for 30 minutes. To this, were added 30.3 parts of dibutyl tin oxide and 5 parts of toluene and the mixture was reacted under reflux condition as in Example 1 to obtain a pale yellow resin having an acid value of 20, Tg of 11° C. and number average molecular weight of 1400. Sn content of this resin was 15.4 wt%. 60 Parts of this resin were dissolved in a combined mixture of 30 parts of xylene and 10 parts of methyl isobutyl ketone to obtain a comparative resinous varnish 5.
- Test plate having a defined thickness of coating was attached to Discrotor, immersed in sea water (18° to 23° C.) and rotated at a constant speed (peripheral speed 35 knots) for 1 year (days and nights). Use-up rate of the coating was determined microscopically.
- the present antifouling paint has an excellent polishing effect.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
(HO--R--CO--O--).sub.l M (I)
(HO--R--CO--O--).sub.l M (I)
--(C.sub.a H.sub.2a)--
--(C.sub.b H.sub.2b-2)--
Cu>Sn>Ni>Zn>Mg>Ba>Ca
TABLE 1 ______________________________________ Example No. 3 4 5 6 7 ______________________________________ Raw materials used Cu 12-HO stearate 31.4 23.1 28.9 39.6 35.2 phthalic anhydride 46.5 40.2 succinic anhydride 27.3 5.3 31.7 adipic acid 9.3 37.2 trimethylolethane 2.1 trimethylolpropane 5.2 neopentylglycol 25.2 26.5 24.6 diethylene glycol 32.0 28.7 dibutyl tin oxid 0.2 0.2 0.2 0.2 0.2 method of Example 2 1 2 1 1 varnish No. V-3 V-4 V-5 V-6 V-7 molecular weight 1100 4400 2800 1200 1600 Tg °C. -5 15 10 8 5 viscosity G P S H J solid % 60.1 55.4 59.2 60.2 59.3 Cu % 3.2 2.3 2.9 4.0 3.4 Sn % 0.1 0.1 0.1 0.1 0.1 ______________________________________
TABLE 2 ______________________________________ initial final hydrolysis hydrolysis wt. mg wt. mg rate (1) rate (2) ______________________________________ V-1 484 329 0.32 184 V-2 462 318 0.31 171 V-3 476 324 0.32 181 V-4 493 453 0.08 48 V-5 504 432 0.14 86 V-6 476 334 0.30 169 V-7 437 314 0.28 146 V-8 485 423 0.12 74 V-9 477 446 0.06 37 V-10 452 305 0.33 175 V-11 487 317 0.35 202 V-12 508 317 0.38 227 V-13 461 340 0.26 144 V-14 470 263 0.44 246 C-1 491 489 0.004 2.4 C-2 474 472 0.004 2.4 C-3 488 409 0.16 94 C-4 462 455 0.015 8.3 C-5 482 127 0.74 427 ______________________________________
TABLE 3 ______________________________________ Prescription of antifouling paint (weight %) ______________________________________ Example 15 16 17 18 19 20 21 ______________________________________ res. varnish V-1 45 V-2 40 V-3 35 50 V-4 40 40 V-5 35 WW rosin vinyl chloride resin VYHH dioctyl phthalate cuprous oxide 35 25 10 35 35 cuprous thiocyanate 20 MANEB 5 5 ZINEB 8 5 5 triphenyl tin 5 10 5 5 10 hydroxide triphenyl tin chloride triphenyl tin 10 5 fluoride ZDMC TMT colcothar 5 5 5 5 5 zinc white 20 20 10 15 methyl isobutyl 5 ketone xylene 5 10 12 15 15 15 white spirit 10 total 100 100 100 100 100 100 100 ______________________________________ Example 22 23 24 25 26 27 28 ______________________________________ res. varnish V-6 45 V-7 45 V-8 60 V-9 45 V-10 40 V-11 40 V-12 45 WW rosin vinyl chloride resin VYHH dioctyl phthalate cuprous oxide 25 30 40 40 40 cuprous thiocyanate MANEB 5 5 ZINEB 5 triphenyl tin 5 hydroxide triphenyl tin chloride triphenyl tin 10 5 10 fluoride ZDMC 10 TMT 5 colcothar 5 5 5 5 zinc white 15 15 20 methyl isobutyl 5 5 5 5 5 ketone xylene 10 10 10 10 10 10 white spirit total 100 100 100 100 100 100 100 ______________________________________ Example Comparative Example 29 30 6 7 8 9 10 ______________________________________ res. varnish V-13 45 V-14 40 C-1 55 C-3 50 C-4 45 C-5 40 WW rosin 7 vinyl chloride 7 resin VYHH dioctyl phthalate 2 cuprous oxide 40 35 35 35 35 40 40 cuprous thiocyanate MANEB 5 5 ZINEB 5 5 triphenyl tin 5 hydroxide triphenyl tin chloride triphenyl tin 3 5 5 fluoride ZDMC TMT colcothar 5 5 10 5 5 5 5 zinc white 10 methyl isobutyl 5 5 15 5 5 ketone xylene 16 10 white spirit total 100 100 100 100 100 100 100 ______________________________________
TABLE 4 ______________________________________ Antifouling test (surface area % adhered with submarine livings) immersed months 3 6 9 12 18 24 30 ______________________________________ Exam. 15 0 0 0 0 0 0 0 16 0 0 0 0 0 0 0 17 0 0 0 0 0 0 0 18 0 0 0 0 0 0 0 19 0 0 0 0 0 0 0 20 0 0 0 0 0 0 0 21 0 0 0 0 0 0 5 22 0 0 0 0 0 0 0 23 0 0 0 0 0 0 0 24 0 0 0 0 0 0 0 25 0 0 0 0 0 5 10 26 0 0 0 0 0 0 0 27 0 0 0 0 0 0 0 28 0 0 0 0 0 0 0 29 0 0 0 0 0 0 0 30 0 0 0 0 0 0 0 Comp. Exam. 6 0 0 0 5 80 100 100 7 0 0 5 20 80 100 100 8 0 0 0 0 5 20 60 9 0 0 0 5 70 100 100 10 0 0 0 0 100* 100* 100* ______________________________________ *anticorrosive coating was exposed because of the complete solution of th anticorrosive coating
TABLE 5 ______________________________________ Coating use-up rate initial film thick. use-up use-up film thick. after 1 yr. rate (1) rate (2) ______________________________________ Exam. 15 210μ 145μ 0.31 65μ 16 220 165 0.25 55 17 190 110 0.42 80 18 220 140 0.36 80 19 210 190 0.10 20 20 210 180 0.13 30 21 190 155 0.18 35 22 230 145 0.37 85 23 190 125 0.34 65 24 220 200 0.09 20 25 210 200 0.05 10 26 230 165 0.28 65 27 190 130 0.32 60 28 240 160 0.33 80 29 200 150 0.25 50 30 220 130 0.41 90 Comp. Exam. 6 200 200 0 0 7 220 220 0 0 8 190 150 0.21 40 9 210 205 0.02 5 10* 230 35 0.91 420 ______________________________________ *result after 6 months (since the coating was wholly dissolved out after months)
Claims (4)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/602,722 US4499223A (en) | 1981-10-17 | 1984-04-23 | Hydrolyzable polyester resins and coating compositions containing the same |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16592381A JPS5867767A (en) | 1981-10-17 | 1981-10-17 | Antifouling paint |
JP16592281A JPS5867722A (en) | 1981-10-17 | 1981-10-17 | Preparation of hydrolyzable polyester resin |
JP16592181A JPS5867761A (en) | 1981-10-17 | 1981-10-17 | Composition for forming coating film of hydrolyzable resin |
US06/602,722 US4499223A (en) | 1981-10-17 | 1984-04-23 | Hydrolyzable polyester resins and coating compositions containing the same |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/426,155 Continuation-In-Part US4482701A (en) | 1981-10-17 | 1982-09-28 | Hydrolyzable polyester resins, varnishes and coating compositions containing the same |
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Publication Number | Publication Date |
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US4499223A true US4499223A (en) | 1985-02-12 |
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Application Number | Title | Priority Date | Filing Date |
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US06/602,722 Expired - Lifetime US4499223A (en) | 1981-10-17 | 1984-04-23 | Hydrolyzable polyester resins and coating compositions containing the same |
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US (1) | US4499223A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4769398A (en) * | 1985-04-18 | 1988-09-06 | Nippon Paint Co., Ltd. | Antifouling coating composition having improved polishing property |
US5518730A (en) | 1992-06-03 | 1996-05-21 | Fuisz Technologies Ltd. | Biodegradable controlled release flash flow melt-spun delivery system |
US6211301B1 (en) * | 1997-09-03 | 2001-04-03 | Kansai Paint Co., Ltd | Method for production of antifouling resin and antifouling resin composition |
US6395866B1 (en) * | 1999-07-27 | 2002-05-28 | Toyo Boseki Kabushiki Kaisha | Polyester resin for antifouling paint and antifouling paint containing the resin |
US20070088099A1 (en) * | 2003-11-17 | 2007-04-19 | Leon Mentink | Use of an aqueous dispersion of at least one biodegradable polymer containing at least one stabilizing agent for the preparation of an aqueous filmogenic composition |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2985624A (en) * | 1956-10-09 | 1961-05-23 | Anaconda Wire & Cable Co | Preparation of zinc polyesters |
US3053783A (en) * | 1958-09-19 | 1962-09-11 | Standard Oil Co | Water soluble polyesters of benzene polycarboxylic acids |
US3075936A (en) * | 1960-03-30 | 1963-01-29 | Standard Oil Co | Surface coating composition of a resinpolyester mixture |
US3761450A (en) * | 1969-09-11 | 1973-09-25 | Hoechst Ag | Salts of polycarboxylic acids as nucleating agents in polyesters |
US4277392A (en) * | 1979-06-01 | 1981-07-07 | Tenneco Chemicals, Inc. | Thickening agents for unsaturated polyester resin compositions |
-
1984
- 1984-04-23 US US06/602,722 patent/US4499223A/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2985624A (en) * | 1956-10-09 | 1961-05-23 | Anaconda Wire & Cable Co | Preparation of zinc polyesters |
US3053783A (en) * | 1958-09-19 | 1962-09-11 | Standard Oil Co | Water soluble polyesters of benzene polycarboxylic acids |
US3075936A (en) * | 1960-03-30 | 1963-01-29 | Standard Oil Co | Surface coating composition of a resinpolyester mixture |
US3761450A (en) * | 1969-09-11 | 1973-09-25 | Hoechst Ag | Salts of polycarboxylic acids as nucleating agents in polyesters |
US4277392A (en) * | 1979-06-01 | 1981-07-07 | Tenneco Chemicals, Inc. | Thickening agents for unsaturated polyester resin compositions |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4769398A (en) * | 1985-04-18 | 1988-09-06 | Nippon Paint Co., Ltd. | Antifouling coating composition having improved polishing property |
US5518730A (en) | 1992-06-03 | 1996-05-21 | Fuisz Technologies Ltd. | Biodegradable controlled release flash flow melt-spun delivery system |
US6211301B1 (en) * | 1997-09-03 | 2001-04-03 | Kansai Paint Co., Ltd | Method for production of antifouling resin and antifouling resin composition |
US6395866B1 (en) * | 1999-07-27 | 2002-05-28 | Toyo Boseki Kabushiki Kaisha | Polyester resin for antifouling paint and antifouling paint containing the resin |
US20070088099A1 (en) * | 2003-11-17 | 2007-04-19 | Leon Mentink | Use of an aqueous dispersion of at least one biodegradable polymer containing at least one stabilizing agent for the preparation of an aqueous filmogenic composition |
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